JP2018508617A - Elastomer silicone emulsion for coating application - Google Patents

Abstract

Silicone-terminated polyether emulsions are used to improve paints and coatings on brick, gypsum, cellulose and EIFS substrates, improve paint and coating flexibility, water repellency and elastomeric properties, moisture paints and coating substrates Protects from cracks caused by penetration. Modified paints and coatings are also used as anti-graffiti materials.

Description

  The present invention relates to improvements in paints and coatings using elastomeric silicone emulsions.

  Most of the building materials are porous, so that the building materials are exposed to external moisture, for example by rain. When the pores of a building material are filled with water, the material insulation is adversely affected. Long-term moisture can also lead to moisture damage. Various coatings on the surface of bricks, gypsum, cellulose and external thermal finishing systems (EIFS) have been developed, but many coatings tend to be brittle. Brittleness can lead to cracks in the coating, and if a large area of the coating film cracks, it becomes nonfunctional and loses value. If water enters the coating or substrate during repeated freezing and thawing, this can also lead to cracking.

  Graffiti on buildings and structures is also a serious problem. Various anti-graffiti materials have been developed that are resistant to the application of spray paint and marker pens, or to aid in the removal of graffiti. Such graffiti prevention materials do not provide satisfactory results and / or are expensive.

  Therefore, there is a long-standing need to deal with defects and the like to solve the above problems. Specifically, the development of paints or coatings as one- and two-part paint systems with improved flexibility and water repellency for such coating applications, and excellent tensile strength, elongation, and water repellency. The need to do has existed for many years.

  After all, there has been a need for many years to develop an effective anti-graffiti coating with excellent water repellency and flexibility.

  Surprisingly and unexpectedly, it has been found that stable emulsions of silicone-terminated polyethers can be used to improve the paints and coatings on the surfaces of brick, gypsum, cellulose and EIFS substrates. Improving paints and coatings with stable emulsions improves the flexibility and elastomeric properties of paints and coatings. Furthermore, such improvements provide excellent water repellency that protects the paint and coating substrate from cracks due to moisture penetration. In addition, here surprisingly and unexpectedly, paints or coatings modified using a stable emulsion of silicone-terminated polyethers show good protective film performance and are effective anti-graffiti coatings Can be used as

Detailed Description of the Invention

  The paint and coating to be improved may be any paint or coating suitable for interior and / or exterior applications, including brick, gypsum, cellulose and EIFS substrate surface coatings, and the like. Paints and coatings for the purposes of the present invention refer to any liquid composition, liquefiable composition, or varnish-like composition that changes to a solid film after application to a substrate. Paints and coatings may be solvent systems such as petroleum or alkyd resin systems; aqueous systems such as aqueous emulsion / latex paints or acrylic paints; high solid paints with low volatile organic compound content; powder coatings; or radiation curable coatings Good.

  Paints or coatings modified with a stable emulsion of silicone-terminated polyethers may contain one or more of the following components: binders, diluents and / or solvents, dyes and / or fillers and additives. Good.

  The binder is a film-forming component of the paint that contributes to the good adhesion of the coating to the substrate. Binders are alkyd resin, acrylic resin, vinyl resin, vinyl / acrylic resin, styrene / acrylic resin, vinyl acetate / ethylene condensation resin, phenol / formaldehyde condensation resin, polyurethane resin, polyester resin, nitrocellulose resin, polyamide resin, melamine Natural or synthetic resins such as resins, epoxy resins or polymerizable oils may be included. Specific examples of the binder may be a water-dilutable solvent-free emulsion of a silicone resin, or a water-dilutable solvent-free emulsion of a polysiloxane modified with a functional silicone resin or a water-dilutable siloxane.

  Diluents or solvents are media in which binders, dyes, and additives are dispersed, and / or media that adjust the viscosity of the paint. Diluents may be water, aliphatic compounds, aromatic compounds, alcohols, ketones, petroleum spirits, turpentine oils, and the like. Specific examples of the solvent include petroleum distillates, esters, glycol esters, xylene, toluene, ethylbenzene, n-butyl acetate, n-butanol, isopropanol, 2-butoxyethanol, dimethylformamide, methyl ethyl ketone, naphthalene, and combinations thereof. There may be. The diluent may also be a reactive diluent that reacts with other binder components or elastomeric silicones.

  Dyes contribute to color or opacity, can be used to protect the substrate from UV light, improve hardness, reduce ductility, and / or adjust gloss. The dye may be a synthetic dye or a natural dye. Specific examples of pigments may include clay, calcium carbonate, mica, silica, talc, calcined clay, precipitated barium sulfate, precipitated calcium carbonate, synthetic calcined silica, etc., or combinations thereof.

Examples of inorganic pigments include sodium silicate, sulfur-containing aluminum (Ultramarine Violet), and a naturally occurring complex of sulfur-containing sodium silicate (Na _8-10 Al ₆ Si ₆ O ₂₄ S _2-4 ) (Ultramarine ); Barium copper pigments such as Chinese purple (BaCuSi ₂ O ₆ ) and dark blue (BaCu ₂ Si ₂ O ₇ ); calcium copper silicate (CaCuSi ₄ O ₁₀ ), copper acetarsenite (Cu (C ₂ H ₃₎ such as manganese ammonium pyrophosphate _(NH 4 _MnP 2 _{O 7)} manganese dye;; O _{2) 2} · 3Cu _{(AsO 2)} copper dye such as synthetic dye _2); barium pigments such as barium sulfate (BaSO ₄₎ tin cobalt _(CoO 3 Sn), nitrite cobalt potassium _(Na 3 Co _{(N 2) 6),} cobalt chromite (CoCr ₂ O _4), cobalt pigments such as cobalt titanate _(Co 2 TiO _4); hexacyanoferrate (II), iron _(III) (Fe 7 _{(CN) 18)} iron oxide ( III) Iron pigments such as naturally occurring clays such as monohydrate (Fe ₂ O ₃ .H ₂ O), anhydrous Fe ₂ O ₃ ; cadmium sulfide (CdS), cadmium selenide (Cd ₂ SSe), Cadmium pigments such as cadmium selenide (CdSe); chromium oxide (Cr ₂ O ₃ ), chromium oxide monohydrate (Cr ₂ O ₃ .H ₂ O) pigment, lead chromate natural pigment (PbCrO ₄ ), lead chromate (II) and lead oxide (II) (PbCrO ₄ + PbO) spontaneous dye mixture composed of; monocrystalline arsenic sulfide _{(as 2 S} 3); lead antimonite ( b _{(SbO 3) 2,} basic lead carbonate _{((PbCO 3) 2 · Pb} (OH) 2) lead pigments such as; carbon pigments such as carbon black; mercury pigments such as mercury sulfide (HgS) antimony trioxide ( Sb ₂ O _3), antimony pigments, such as; zinc pigments such as zinc oxide (ZnO) or zinc chromate (ZnCrO _4); nickel antimony titanium yellow rutile _{(NiO · Sb 2 O 3 ·} 20TiO 2) or titanium dioxide (TiO ₂ ) And the like; and a complex of sulfur-containing sodium silicate (Na _8-10 Al ₆ Si ₆ O ₂₄ S _2-4 ) containing blue gold stone known as ultramarine blue.

Examples of organic dyes include diarylide aniline yellow dyes; benzimidazole yellow dyes; heterocyclic yellow dyes; allylide yellow, isoindoline yellow, tetrachloroisoindolinone yellow, azomethine yellow, quinophthalone yellow, or triazinyl yellow, Disazo condensate yellow dyes such as naphthol orange, carion red, benzimidazolone orange; phthalocyanine green dyes having a chemical formula in the range of C ₃₂ H ₃ Cl ₁₃ CuN _{8 to} C ₃₂ H ₃ Cl ₁₃ CuN ₈ , copper Phthalocyanine; 8,18-dichloro-5,15-diethyl-5,15-dihydrodiindolo (3,2-b: 3 ′, 2′-m) tri-phenodioxazine and the like such as dioxazine violet It is below.

  The dye may optionally include an opaque dye to protect the substrate from UV light, such as silica / alumina / zirconium coated titanium dioxide, phthalocyanine blue dye, or red iron oxide.

  Fillers may be used to thicken the film, strengthen the binder, impart texture to the paint, and / or increase the bulk of the paint. Fillers include diatomaceous earth, talc, lime, barium sulfate, clay, kaolin clay, precipitated calcium carbonate or heavy calcium carbonate, chalk, limestone, marble, magnesium carbonate, dolomite, fine quartz, silicate, etc. A combination thereof may be included.

  Additives may include, for example, surface tension, flow properties, and leveling properties, appearance, gloss, texture improvement, wet edge properties and / or antifreeze properties, improved pigment stability, foaming and / or skin tension control, Improved rheology, improved scratch resistance, catalyst, desiccant, thickener, stabilizer, emulsifier, texturizer, adhesion promoter, UV stabilizer, rust inhibitor, texturizer, matting agent, biocide, It can perform various functions such as bactericides, insecticides, algicides, or combinations thereof.

  Examples of additives include silicone polyether copolymers, dispersions of high molecular weight polysiloxanes or polydimethylsiloxanes, silicone surfactants, ethylene oxide surfactants, as additives that improve scratch resistance and impart or improve lubricity Agents; silicone emulsifiers, fluorosilicones, organo-modified silicone copolymers as additives to control foaming; aminopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, cationic vinylbenzyl and amino-functional methoxysilane, glycid Xylpropyltrimethoxysilane, silanol functional additive, amino-functional silicone polymer as adhesion promoter and dye treatment additive; silane / siloxane blend as additive to promote water resistance; aryl Lukyl-modified silicone, silicone polyether copolymer as an additive to improve leveling and gloss; silicone elastomer particles with epoxy functionality to improve wear resistance, impart smoothness and matte finish; promote substrate wettability Silicone polyether copolymer as additive; 2,2 ′-(2,5-thiophenediyl) bis (5-tert-butylbenzoxazole) as optical brightener; 2- [2 as UV light absorber -Hydroxy-3,5-di- (1,1-dimethylbenzyl)]-2H-benzotriazole, 2- (2H-benzotriazol-2-yl) -4-methylphenyl; Tris (2 , 4-Di-tert-butylphenyl) phosphite, stearyl-3- (3 ′, 5′-di tert-butyl-4-hydroxyphenyl) propionate, 2,2′-methylenebis (4-methyl-6-tert-butylphenol); tetrachloroisophthalonitrile as biocide, 3-iodo-2-propynylbutylcarbamate 2-n-octyl-4-isothiazolin-3-one, diiodomethyl-p-trisulfone, N- (trimethylthio) phthalamine, 1,2-benzisothiazolin-3-one; 2- as a fungicide / algicide (4-thiazolyl) (benzimidazole), dichlorooctyl isothiazolone; potassium sodium phosphate as buffer; hydrophobic copolymer polyelectrolyte as dye dispersant; modified hydroxyethyl cellulose as thickener; modified polyol as antifoam As a fusion aid Ester alcohols; calcium carbonate as extender; talc as additive to impart dispersibility, firmness, anti-cracking and barrier properties to the pigment; aqueous butyl acrylate styrene copolymer for dispersion; and (( Mention may be made of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and hydrous acetic acid. Any other additive for interior and exterior paints is also contemplated.

  Elastomer silicone emulsions added as modifiers to paints or coatings are oil-in-water emulsions. Such emulsions are made by dispersing organopolysiloxane ("silicone") in water with the aid of a surfactant or dispersant. Many different types of surfactants or “emulsifiers” can be used, including anionic surfactants, cationic surfactants, zwitterionic surfactants, and nonionic surfactants, especially the latter Including. Inorganic particles that are partially hydrophobic in the nanometer size range can also be used, and these particles contain both hydrophobic and hydrophilic portions similar to conventional surfactant structures.

（式中、
Ｒ^１は、アルキル、アリール、好ましくはメチル基であり、
Ｒ^２は、Ｃ_１−Ｃ_１２−アルキル、好ましくはメチル、またはエチル基、グリコール、Ｈ、またはアリールであり、
Ｘは、Ｏ、ＮＲ^３（式中、Ｒ^３は、Ｈ、Ｃ_１−Ｃ_１２−アルキルまたはアリールである）、好ましくは、ＸはＯであり、
Ｙは、−（ＣＨ_２）_３−、−（ＣＨ_２）_３ＮＨＣ（＝Ｏ）−、−ＣＨ_２、−ＣＨ_２ＮＨＣ（＝Ｏ）−（式中、ＹはＳｉ−Ｃ結合しており、好ましくはＹ＝−（ＣＨ_２）_３ＮＨＣ（＝Ｏ）−、−ＣＨ_２ＮＨＣ（＝Ｏ）−、より好ましくは、Ｙ＝−ＣＨ_２ＮＨＣ（＝Ｏ）−である）であり、
Ｍは、独立して−ＣＨ_２ＣＨ_２−、−ＣＨ_２ＣＨ（ＣＨ_３）−、−ＣＨ_２ＣＨ_２ＣＨ_２ＣＨ_２−、好ましくは、−ＣＨ_２ＣＨ（ＣＨ_３）−であり、前記全Ｍの過半数は−ＣＨ_２ＣＨ（ＣＨ_３）−であり、前記過半数は５０％以上を意味し、好ましくは、全Ｍの６０％以上、７０％以上、８０％以上、または９０％以上で、ＭはＣＨ_２ＣＨ（ＣＨ_３）−であり、
ｎは、０〜２、好ましくは、１であり、
ｍは、１〜５００、好ましくは、１０〜３０である）、ならびに
所望により（Ｂ）式（ＩＩ）の単位を含むアルコキシ−シリコーン化合物

（式中、
ａは、０〜３、好ましくは１であり、
ｂは、０〜２、好ましくは０であり、
ｃは、０、１、２または３、好ましくは３であり、
Ｒ^４は、アルキル、アリール、アミノアルキル、グリシドキシアルキル、メルカプトアルキルであり、
Ｒ^５は、アルキル、アリールであり、
Ｒ^６は、アルキル、Ｈ、エチレンオキシド、プロピレンオキシドであり、
但し、ａ＋ｂ＋ｃは４以下であり、オリゴマー、ポリマーに相当し、好ましくは、ａ＋ｂ＋ｃは４未満であり、オリゴマーまたはポリマーに相当する）、ならびに
所望により、（Ｃ）乳化剤、
（Ｄ）水、
さらに、所望により、
（Ｅ）触媒、
（Ｆ）充填剤、および
（Ｇ）他の添加剤
を含むエマルションであってもよい。 The emulsion added as a modifier to the paint or coating comprises (A) a silyl-terminated polymer of formula (I) and an alkoxy-silicone compound as essential elements,
(A) Silyl-terminated polymer of formula (I)

(Where
R ¹ is alkyl, aryl, preferably a methyl group,
R ² is C ₁ -C ₁₂ -alkyl, preferably a methyl or ethyl group, glycol, H or aryl;
X is O, NR ³ (wherein R ³ is H, C ₁ -C ₁₂ -alkyl or aryl), preferably X is O;
Y _{is, - (CH 2) 3 -} , - (CH 2) 3 NHC (= O) -, - CH 2, -CH 2 NHC (= O) - (In the formula, Y is bonded Si-C , Preferably Y = — (CH ₂ ) ₃ NHC (═O) —, —CH ₂ NHC (═O) —, more preferably Y = —CH ₂ NHC (═O) —).
M is independently —CH ₂ CH ₂ —, —CH ₂ CH (CH ₃ ) —, —CH ₂ CH ₂ CH ₂ CH ₂ —, preferably —CH ₂ CH (CH ₃ ) —, The majority of all M is —CH ₂ CH (CH ₃ ) —, and the majority means 50% or more, preferably 60% or more, 70% or more, 80% or more, or 90% or more of all M. , M is CH ₂ CH (CH ₃ ) —
n is 0-2, preferably 1,
m is 1 to 500, preferably 10 to 30), and optionally (B) an alkoxy-silicone compound comprising units of formula (II)

(Where
a is 0 to 3, preferably 1.
b is 0 to 2, preferably 0;
c is 0, 1, 2 or 3, preferably 3,
R ⁴ is alkyl, aryl, aminoalkyl, glycidoxyalkyl, mercaptoalkyl,
R ⁵ is alkyl or aryl;
R ⁶ is alkyl, H, ethylene oxide, propylene oxide,
Provided that a + b + c is 4 or less and corresponds to an oligomer or a polymer, preferably a + b + c is less than 4 and corresponds to an oligomer or a polymer), and optionally (C) an emulsifier,
(D) water,
In addition, if desired
(E) catalyst,
It may be an emulsion containing (F) a filler, and (G) another additive.

Specific examples of emulsions useful as paint or coating modifiers include the following component (A), a silane-terminated polymer binder, about 0.25-0.3 mmol / g or 0.4-0. It may consist of dimethoxymethylsilylmethyl carbamate-terminated polyether with a methyl group content of 5 mmol / g.

  This silane-terminated polymer with dimethoxymethylsilylmethylcarbamate end groups is a clear, colorless viscous oil that hydrolyzes in the presence of moisture to form silanols and then reacts with itself to stabilize Siloxane bonds are formed. The nitrogen atom adjacent to the silicone atom in the dimethoxymethylsilylmethylcarbamate group greatly accelerates the hydrolysis of the alkoxysilyl group. The silane terminated polyether may have a molecular weight of 12,000 g / mol to 18,000 g / mol and a viscosity of 10,000 cps to 30,000 cps.

  Instead, the emulsion contains the following exemplary silane-terminated polymer binder as component (A), alone or from 0.5 to 0.7 mmol / g or from 0.35 to 0.45 mmol / g methoxy content: May be included in combination with trimethoxysilylpropyl carbamate having The weight percent of the polymer binder may be 15-60% of the total loading, more preferably 40-55%, most preferably 52%.

The dimethoxymethylsilylmethyl carbamate-terminated polymer used in the following examples has the following properties: density 1.0069 g / cm ³ at 20 ° C. measured according to DIN 51757, flash point 98 ° C. measured according to ISO 2719, measured according to DIN 51562 A dynamic viscosity of 10,000 mPas at 25 ° C. and a methoxy group content of 0.4 to 0.5 mmol / g. Another dimethoxymethylsilylmethylcarbamate-terminated polyether used in the following examples is designated as dimethoxymethylsilylmethylcarbamate-terminated polymer 2 and has the following properties: density 1.0064 g / 25 ° C. measured according to DIN 51757 cm ³ , a flash point of 250 ° C. or higher measured according to ISO 2592, a dynamic viscosity of 10,000 mPas at 25 ° C. measured according to DIN 51562, and a methoxy group content of 0.5 to 0.7 mmol / g.

  The emulsion also includes a polymeric binder, component (A), such as dimethoxymethylsilylmethylcarbamate terminated polyether, and one or more silicone resins; component (B), eg, having a narrow molecular weight distribution and compatible silicone It may be composed of solvent-free reactive methoxy functional methylphenyl polysiloxane which is very suitable for introducing components into other binder systems to improve weatherability or heat resistance. The methoxy-functional methylphenyl polysiloxane is a clear liquid with a total silicone content of 98% by weight or more, an alkoxy content of 15% by weight or more, and a solvent content of less than 2% by weight. The weight percentage of the silicone resin in the premix with the polymer conjugate may be 20-70%, preferably 40-60%.

Alternatively, the emulsion may contain the following exemplary silicone resin as component B: Mw = 6600 g / mol, Mn = 2000 g / mol, Mw / Mn = 3.3, (MeSiO _3/2 ) _0.88 (MeSi (OH) O _2/2 ) _0.05 (MeSi (OEt) O _2/2 ) _0.06 (Me ₂ SiO _2/2 ) _0.01 ,

Mw = 10000 g / mol, Mn = 2300 g / mol, Mw / Mn = 4.3, (MeSiO _3/2 ) _0.86 (MeSi (OH) O _2/2 ) _0.02 (MeSi (OEt) O _2/2 ) _0.10 (Me ₂ SiO _2/2 ) _0.02 ,

Mw = 4500 g / mol, Mn = 1900 g / mol, Mw / Mn = 2.4, (MeSiO _3/2 ) _0.71 (MeSi (OH) O _2/2 ) _0.03 (MeSi (OEt) O _2/2 ) _0.05 (Me ₂ SiO _2/2 ) _0.21 ,

Mw = 9000 g / mol, Mn = 2300 g / mol, Mw / Mn = 3.9, (MeSiO _3/2 ) _0.88 (MeSi (OH) O _2/2 ) _0.05 (MeSi (OMe) O _2/2 ) _0.06 (Me ₂ SiO _2/2 ) _0.01 ,

Mw = 3250 g / mol, Mn = 1300 g / mol, Mw / Mn = 2.5, (MeSiO _3/2 ) _0.33 (MeSi (OH) O _2/2 ) _0.05 (MeSi (OEt) O _2/2 ) _0.01 (Me ₂ SiO _2/2 ) _0.06 (PhSiO _3/2 ) _0.24 (PhSi (OH) O _2/2 ) _0.28 (PhSi (OEt) O _2/2 ) _0.03 ,

Mw = 4700 g / mol, Mn = 1800 g / mol, Mw / Mn = 2.6, (MeSiO _3/2 ) _0.34 (MeSi (OH) O _2/2 ) _0.03 (MeSi (OEt) O _2/2 ) _0.02 (PhSiO _3/2 ) _0.45 (PhSi (OH) O _2/2 ) _0.13 (PhSi (OEt) O _2/2 ) _0.03 ,

Mw = 2400 g / mol, Mn = 1200 g / mol, Mw / Mn = 2.0, (MeSiO _3/2 ) _0.27 (MeSi (OH) O _2/2 ) _0.03 (PhSiO _3/2 ) _0.34 (PhSi (OH) O _2/2 ) _0.14 PhSi (OEt) O _2/2 ) _0.02 (PhMeSiO _2/2 ) _0.17 (PhMeSi (OH) O _1/2 ) _0.03 ,

Mw = 2900 g / mol, Mn = 1500 g / mol, Mw / Mn = 1.9, (PhSiO _3/2 ) _0.45 (PhSi (OH) O _2/2 ) _0.44 PhSi ( OEt) O _2/2 ) _0.09 (PhSi (OH) ₂ O _1/2 ) _0.02 ,

Mw = 1800 g / mol, Mn = 1250 g / mol, Mw / Mn = 1.4, (PhSiO _3/2 ) _0.48 (PhSi (OH) O _2/2 ) _0.17 (PhSi (OEt) O _2/2 ) _0.02 (CH ₃ (CH ₂ ) ₂ SiO _3/2 ) _0.25 (CH ₃ (CH ₂ ) ₂ Si (OH) O _2/2 ) _0.08 ,

Mw = 1700 g / mol, Mn = 1200 g / mol, Mw / Mn = 1.4, (MeSiO _3/2 ) _0.32 (MeSi (OH) O _2/2 ) _0.06 (MeSi (OEt) O _2/2 ) _0.01 (Me ₂ SiO _2/2 ) _0.06 (PhSiO _3/2 ) _0.23 (PhSi (OH) O _2/2 ) _0.29 (PhSi (OEt) O _2/2 ) _0.03 ,

(PhSiO _3/2 ) _0.50 (PhSi (OH) O _2/2 ) _0.15 (PhSi (OEt), 2800 g / mol, Mn = 1200 g / mol, Mw / Mn = 2.3 ) O _2/2 ) _0.02 (CH ₃ (CH ₂ ) ₂ SiO _3/2 ) _0.26 (CH ₃ (CH ₂ ) ₂ Si (OH) O _2/2 ) _0.07 ,

Mw = 6500 g / mol, Mn = 1900 g / mol, Mw / Mn = 3.4, (MeSiO _3/2 ) _0.81 (MeSi (OH) O _2/2 ) _0.04 (MeSi (OEt) O _2/2 ) _0.05 (Me ₂ SiO _2/2 ) _0.10 (wherein Me is a methyl group, Et is an ethyl group, and Ph is a phenyl group).

Another non-limiting example of component B is Mw = 7400 g / mol, Mn = 3100 g / mol, Mw / Mn = 2.4, (SiO _4/2 ) _0.50 (Me ₃ SiO _1/2 ) _0.39 (Si (OEt) O _3/2 ) _0.06 (Si (OEt) ₂ O _2/2 ) _0.02 (Si (OEt) ₃ O _1/2 ) _0.01 ( Si (OH) O _3/2 ) _0.02 ,

Mw = 1400 g / mol, Mn = 900 g / mol, Mw / Mn = 1.6, (SiO _4/2 ) _0.46 (Me ₃ SiO _1/2 ) _0.43 (Si (OEt ) O _3/2 ) _0.07 (Si (OEt) ₂ O _2/2 ) _0.02 (Si (OEt) ₃ O _1/2 ) _0.01 (Si (OH) O _3/2 ) _0.01 ,

Mw = 5300 g / mol, Mn = 2600 g / mol, Mw / Mn = 2.0, (SiO _4/2 ) _0.46 (Me ₃ SiO _1/2 ) _0.37 (ViMe ₂ SiO _1/2 ) _0.06 (Si (OEt) O _3/2 ) _0.07 (Si (OEt) ₂ O _2/2 ) _0.02 (Si (OEt) ₃ O _1/2 ) _0.01 (Si (OH) O _3/2 ) _0.04 ,

Mw = 2600 g / mol, Mn = 1600 g / mol, Mw / Mn = 1.6, (SiO _4/2 ) _0.38 (Me ₃ SiO _1/2 ) _0.42 (ViMe ₂ SiO _1/2 ) _0.06 (Si (OEt) O _3/2 ) _0.07 (Si (OEt) ₂ O _2/2 ) _0.02 (Si (OEt) ₃ O _1/2 ) _0.01 (Si (OH) O _3/2 ) _0.04 ,

Mw = 2400 g / mol, Mn = 900 g / mol, Mw / Mn = 2.7, (MeSiO _3/2 ) _0.37 (MeSi (OEt) O _2/2 ) _0.46 (MeSi (OEt) ₂ O _1/2 ) _0.17 ,

Mw = 2300 g / mol, Mn = 600 g / mol, Mw / Mn = 3.8, (MeSiO _3/2 ) _0.29 (MeSi (OH) O _2/2 ) _0.01 (MeSi (OMe) O _2/2 ) _0.47 (MeSi (OMe) ₂ O _1/2 ) _0.23 ,

Mw = 3300 g / mol, Mn = 900 g / mol, Mw / Mn = 3.7, (MeSiO _3/2 ) _0.32 (MeSi (OMe) O _2/2 ) _0.48 (MeSi (OMe) ₂ O _1/2 ) _0.20 ; Mw = 1000 g / mol, Mn = 700 g / mol, Mw / Mn = 1.4, (PhSiO _3/2 ) _0.23 (PhSi (OMe) O _2/2 ) _0.51 (PhSi (OMe) ₂ O _1/2 ) _0.26 ,

Mw = 1800 g / mol, Mn = 900 g / mol, Mw / Mn = 2.0, (MeSiO _3/2 ) _0.10 (MeSi (OMe) O _2/2 ) _0.17 (MeSi (OMe) ₂ O _1/2 ) _0.03 (PhSiO _3/2 ) _0.15 (PhSi (OMe) O _2/2 ) _0.31 (PhSi (OMe) ₂ O _1/2 ) _0.20 (Me ₂ SiO _2/2 ) _0.04 ,

Mw = 1400 g / mol, Mn = 800 g / mol, Mw / Mn = 1.8, (MeSiO _3/2 ) _0.10 (MeSi (OMe) O _2/2 ) _0.15 (MeSi (OMe) ₂ O _1/2 ) _0.03 (MeSi (O (CH ₂ ) ₃ CH ₃ ) O _2/2 ) _0.03 (PhSiO _3/2 ) _0.15 (PhSi (OMe) O _{2/2 0.24} (PhSi (OMe) ₂ O _1/2 ) _0.15 (PhSi (O (CH ₂ ) ₃ CH ₃ ) O _2/2 ) _0.06 (PhSi (OMe) (O (CH ₂ ) ₃ CH ₃ ) O _1/2 ) _0.04 (PhSi (O (CH ₂ ) ₃ CH ₃ ) ₂ O _1/2 ) _0.01 (Me ₂ SiO _2/2 ) _0.04 ,

Mw = 3000 g / mol, Mn = 1500 g / mol, Mw / Mn = 2.0, (i-OctSi (OMe) (OH) O _1/2 ) _0.01 (i-OctSi (OMe ) O _2/2 ) _0.10 (i-OctSi (OMe) ₂ O _1/2 ) _0.16 (MeSiO _3/2 ) _0.26 (MeSi (OMe) O _2/2 ) _0.36 (MeSi ( OMe) ₂ O _1/2 ) _0.11 ,

Mw = 1000 g / mol, Mn = 800 g / mol, Mw / Mn = 1.2, (Si (OEt) ₂ O _2/2 ) _0.42 (Si (OEt) O _3/2 ) _0.19 (Si (OEt) ₃ O _1/2 ) _0.39 ,

Mw = 1400 g / mol, Mn = 900 g / mol, Mw / Mn = 1.6, (Si (OEt) ₂ O _2/2 ) _0.48 (Si (OEt) O _3/2 ) _0.35 (Si (OEt) ₃ O _1/2 ) _0.09 (SiO _4/2 ) _0.08 ,

Mw = 1400 g / mol, Mn = 600 g / mol, Mw / Mn = 2.3, (MeSiO _3/2 ) _0.23 (i-OctSiO _3/2 ) _0.06 (MeSi (OMe ) O _2/2 ) _0.35 (i-OctSi (OMe) O _2/2 ) _0.09 (MeSi (OEt) ₂ O _1/2 ) _0.19 (i-OctSi (OEt) ₂ O _{1/2 0.08} and

Mw = 1500 g / mol, Mn = 650 g / mol, Mw / Mn = 2.3, (MeSiO _3/2 ) _0.22 (i-OctSiO _3/2 ) _0.05 (MeSi (OH ) O _2/2 ) _0.01 (MeSi (OMe) O _2/2 ) _0.33 (i-OctSi (OMe) O _2/2 ) _0.11 (MeSi (OMe) ₂ O _1/2 ) _{0. 20} (i-OctSi (OMe) ₂ O _1/2 ) _0.08 (wherein Me is a methyl group, Vi is a vinyl group, Et is an ethyl group, and i-Oct is 2, 4, 4-trimethylpentyl group and Ph is a phenyl group).

Methylphenyl silicone resin used in the following examples were measured in accordance with DIN 51562, dynamic viscosity of 280 mm ² / s at 25 ° C., alkoxy content 15% by weight, dynamic viscosity of 280 mm ² / s at 25 ° C., and A methoxy-functional methylphenyl polysiloxane having a total silicone content of 84% by weight.

The emulsion may further contain a long chain alkylalkoxysilane. Long chain is meant a relatively long chain of atoms, preferably a _C 8 _{-C 30,} more preferably _C 12 _{-C 30.} Another example of component B is n-octyltrimethoxysilane, n-octyltriethoxysilane, 2,4,4-trimethylpentyltrimethoxysilane, 2,4,4-trimethylpentyltrimethyl when a + b + c is 4. Ethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, n-nonacosyltriethoxysilane, n-nonacosyltrimethoxysilane, n-triacontyltrimethoxysilane, and n-triacontyltriethoxysilane, hexadecyl Methyldimethoxysilane, hexadecylmethyldiethoxysilane, 2,4,4- (trimethyl-pentyl) methyldimethoxysilane, 2,4,4- (trimethyl-pentyl) methyldiethoxysilane, n-octylmethyldimethoxysilane, 2 , 4,4- (G Ethyl - pentyl) methyl diethoxy silane, n- octyl methyl di-methoxy silane and n- octyl methyl diethoxy silane.

  Component (C), the emulsifier, may be any suitable ionic emulsifier, nonionic emulsifier, gemini emulsifier, or amphoteric emulsifier, or may be in the form of a mixture of different emulsifiers. . The emulsifier may be used in pure form of the material alone or in the form of a solution of one or more emulsifiers in water or in an organic solvent.

  Examples of suitable nonionic emulsifiers are as follows:

  Alkyl sulfates, in particular alkyl sulfates having a chain length of 8 to 18 carbon atoms, 8 to 18 carbon atoms in a hydrophobic group, 1 to 40 ethylene oxide (EO) and / or propylene oxide Alkyl and alkaryl ether sulfates having (PO) units.

  Sulfonsan salts, especially alkyl sulfonates having 8 to 18 carbon atoms, alkylaryl sulfonates having 8 to 18 carbon atoms, taurides, esters containing monoesters of sulfosuccinic acid and monohydric alcohols The alkylphenols having 4 to 15 carbon atoms, and if desired, these alcohols or alkylphenols may be ethoxylated with 1 to 40 EO units.

  Alkali metal salts and ammonium salts of carboxylic acids having 8 to 20 carbon atoms in the alkyl group, aryl group, alkaryl group, or aralkyl group.

  Phosphoric acid partial esters and their alkali metal and ammonium salts, in particular alkyl and alkaryl phosphates having 8 to 20 carbon atoms in the organic group, 8 to 20 carbon atoms in the alkyl or alkaryl group And alkyl ether phosphates and alkyl aryl ether phosphates having 1 to 40 EO units.

  Examples of nonionic emulsifiers are as follows.

  Polyvinyl alcohol further comprising 5 to 50%, preferably 8 to 20% vinyl acetate units and having a degree of polymerization of 500 to 3000.

  An alkyl polyglycol ether, preferably an alkyl polyglycol ether having 3 to 40 EO units and an alkyl group having 8 to 20 carbon atoms.

  Alkyl aryl polyglycol ethers, preferably 5 to 40 EO units, and alkyl aryl polyglycol ethers having 8 to 20 carbon atoms in the alkyl and aryl groups.

  Ethylene oxide / propylene oxide (EO / PO) block copolymer, preferably a block copolymer having 8 to 40 EO / PO units.

  An addition compound of an alkylamine having an alkyl group having 8 to 22 carbon atoms and ethylene oxide or propylene oxide.

  Fatty acids having 6 to 24 carbon atoms.

In the general formula ^R * _{-O-Z o} alkyl polyglycosides (formula, ^{R *} is an average carbon number from 8 to 24 linear or branched, saturated or unsaturated alkyl group, _{Z o} is the average o = An oligoglycoside group comprising 1 to 10 hexose or pentose units or a mixture thereof).

  Natural substances and derivatives thereof, such as lecithin, lanolin, saponin, cellulose, and cellulose alkyl ethers and carboxyalkyl celluloses, each of which has up to 4 carbon atoms in its alkyl group.

  In particular, a straight-chain organo (containing an element O, N, C, S, P, Si, in particular having an alkoxy group with a maximum of 24 carbon atoms and / or a maximum of 40 EO and / or PO groups ( Poly) siloxane-containing polar groups.

  Examples of cationic emulsions are as follows.

  Salts of primary aliphatic amines, secondary aliphatic amines, and tertiary aliphatic amines having 8 to 24 carbon atoms with acetic acid, sulfonic acid, hydrochloric acid, and phosphonic acid.

  Quaternary alkylammonium and alkylbenzeneammonium salts, particularly those in which the alkyl group has 6 to 24 carbon atoms, specifically halides, sulfates, phosphates, and acetates.

  Alkyl pyridinium salts, alkyl imidazolinium salts, and alkyl oxazolinium salts, particularly those in which the alkyl chain has a maximum of 18 carbon atoms, specifically halides, sulfates, phosphates And acetate.

  Particularly preferred is a combination of a surfactant and at least one emulsifier having 16 or more EO units.

  Specific examples of useful emulsifiers include ethoxylated isotridecanol, ethoxylated castor oil, ethoxylated nonionic emulsifiers made from saturated iso-C13 alcohol, nonionic secondary alcohol ethoxylates such as octylphenol ethoxylate Or a combination thereof, in particular a blend of ethoxylated castor oil and an ethoxylated nonionic emulsifier made from saturated iso-C13 alcohol. The weight% of the emulsifier may be 1-15% by weight of the total weight of the formulation, more preferably 2-10% by weight and most preferably 4% by weight.

  Non-limiting examples of optional catalyst component (E) are all known condensation catalysts, such as aluminum (III) neodecanoate, aluminum (III) stearate, aluminum (III) ethoxide, aluminum (III) octoate, Aluminum (III) ethyl hexanoate, aluminum (III) propoxide, aluminum (III) butoxide, aluminum (III) acetylacetonate, aluminum (III)-(9-octadecenyl acetoacetate) diisopropoxide, Zinc (II) stearate, zinc (II) octoate, zinc (II)-(2-ethylhexanoate), zinc (II)-(acetylacetonate), zinc (II) -bis (2,2,6) , 6-Teramethyl-3,5-heptaneone G), strontium (II)-(2-ethylhexanoate), titanium (IV) -bis (ethyl acetoacetate) -bis (isobutanolate), titanium (IV)-(n-butoxide), titanium (IV)- (T-butoxide), zirconium (IV) acetylacetonate, zirconium (IV)-(2-ethylhexanoate), zirconium (IV) lactate, lithium (I) -octanoate, bismuth (III) neodecanoate, dioctyltin ( IV) laurate, dibutyltin (IV) laurate, dimethyltin (IV) laurate, dioctyltin (IV) oxide, dibutyltin (IV) oxide, dimethyltin (IV) oxide, dioctyltin (IV) acetate, dibutyltin (IV) acetate, geo Compound obtained by reaction of tiltin (IV) acetate and tetraethoxysilane, composition obtained by reaction of dibutyltin (IV) acetate and tetraethoxysilane, tin (II) octoate, lead (II) acetate, lead (II ) Octoate, lead (II) oxide, lead (II) sulfide, lead (II) carbonate, nickel (II) acetylacetonate, nickel (II) acetate, nickel (II) octoate, nickel (II) carbonate, cobalt (II) ) Metal compounds such as octoate, cobalt (II) carbonate, manganese (II) octoate, manganese (II) carbonate, manganese (IV) oxide; carboxylic acids, dicarboxylic acids, organophosphoric acids, and their mono- and di-esters , Phosphonic acids and their monoesters, as well as acids such as diorganophosphoric acid, boric acid, boron (III) fluoride, ammonium salts of carboxylic acids, and anhydrides; alkali and alkaline earth metal hydroxides, alkali and alkali Earth metals and bases such as butyl lithium; triorganyloxyamine, monoorganylamine, diorganylamine (piperidine, piperazine (1,4-diazacyclohexane), pyrrolidine, homopiperazine (1,4-diazepane) 7-azabicyclo [2.2.1] heptane or bispidine), triorganylamine (and DABCO (1,4-diazabicyclo [2.2.2] octane)), 4,5-dihydro-1H-imidazole, 2-Organyl-4,5-dihydro-1H-imidazo 1,4-diazabicyclo [2.2.2] octane, optionally zinc chelates, and organylamidines, 1,4,5,6-tetrahydropyrimidine, 2-organyl-1,4,5,6 -Tetrahydropyrimidine, 1.5-diazabicyclo [4.3.0] non-5-ene, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5,7-triazabicyclo [ 4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene, aminomethaneamidine, 1-methylguanidine, N, N '-Dimethylguanidine, N, N, N', N'-tetramethylguanidine, N, N, N ', N'-tetramethylN' '-aryl-guanidine, N, N, N', N'-tetra Methyl-N ″-[4 Morpholinyl - (phenylimino) methyl] guanidine, 1-methyl-3-nitroguanidine, 1,8-bis (tetramethylguanidino) naphthalene and guanyl guanidine, such as an amine such as 1-methyl-guanyl guanidine and the like.

  Component (F), which is a filler, may be any of the above fillers.

  Furthermore, non-limiting examples of component (G), such as pigments, stabilizers, preservatives, that are additives used in the emulsions of the present invention include any of the above-mentioned additives. Specific examples of additives useful in the present invention include polyisobutylene as a plasticizer, poly (propylene glycol), or N-dimethoxy (methyl) silylmethyl-O-methyl-carbamate to prevent premature curing .

  Furthermore, the reactive amino freed may be used in the form of an emulsion. Particular examples of amino frees useful in the present invention include reactive aminoethylaminopropyl functional polydimethylsiloxanes.

  Methods for preparing exemplary elastomeric silicone emulsions of the above general formula are described in Examples 1-12 below.

Example 1: Preparation of dimethoxy (methyl) silylmethylcarbamate terminated polyether emulsion

  The emulsion was prepared according to the method utilizing the following composition and weight percent.

  The emulsion of Example 1 was prepared by the following steps.

  The emulsifier, ethoxylated isotridecanol, was mixed with water previously agitated with a Turrax® mixer until a foamy meringue was formed. Dimethoxy (methyl) silylmethylcarbamate terminated polyether was mixed into meringue at 10,000 rpm for 4 minutes. Deionized water was added at 5,000 rpm for 1 minute. Additional deionized water was added for 1 minute at 5,000 rpm. Thereafter, additional deionized water was added at 5,000 rpm for 1 minute.

  The tensile strength and elongation of the emulsion of Example 1 was measured by the method described in ASTM D 2370 using a 75 mm × 13 mm sample shape, the grip separation was 2.54 cm (1.0 inch), and the crosshead speed. Was set to 0.042 cm / second (1.0 inch / minute). The tensile strength of the emulsion of Example 1 was measured to be 599.84 kPa (87 psi), and the elongation was measured to be 40%.

Example 2: Preparation of an emulsion from a blend of dimethoxy (methyl) silylmethyl carbamate terminated polyether and methoxy functional methylphenyl polysiloxane

  The emulsion of Example 1 was prepared by the above method using the following composition and weight percent. A preblended polymer blend of dimethoxy (methyl) silylmethylcarbamate terminated polyether and methoxy functional methylphenylpolysiloxane was prepared instead of only dimethoxy (methyl) silylmethylcarbamate terminated polyether.

  The tensile strength and elongation of the emulsion of Example 2 was measured by the method described in ASTM D 2370 using a 75 mm × 13 mm sample shape, the grip separation was 2.54 cm (1.0 inch), and the crosshead speed. Was set to 0.042 cm / second (1.0 inch / minute). The tensile strength of the emulsion of Example 2 was measured to be 186.158 kPa (27 psi), and the elongation was measured to be 172%.

（式中、
Ｒはイソ−Ｃ_１３Ｈ_２７を表し、
ｘは１〜２０、好ましくは５〜１６の範囲である）
に、適合する飽和イソ−Ｃ１３アルコールから作られるエトキシ化非イオン性界面活性剤とブレンドされたエトキシ化ヒマシ油などの別の乳化剤を利用して、上記の方法により、実施例１および実施例２と、実質的に同じ特性を有する乳化剤を調製することができる。 The following structural formula:

(Where
R represents an iso _-C 13 _{H 27,}
x is in the range of 1-20, preferably 5-16)
Example 1 and Example 2 by the above method utilizing another emulsifier such as ethoxylated castor oil blended with an ethoxylated nonionic surfactant made from a compatible saturated iso-C13 alcohol. And emulsifiers having substantially the same properties can be prepared.

  Instead of ethoxylated isotridecanol, exemplary emulsifiers that can be used in the emulsions of the present invention, particularly the emulsions of Examples 1 and 2, can be prepared as follows.

  The emulsion of the present invention is useful for one-part type and two-part type. Incorporating an emulsion into a paint or coating increases the flexibility and elastomeric properties of the paint or coating, reduces cracking of the painted substrate, and improves the long-term appearance and life of the paint or coating. . In addition, the paint or coating obtains good water resistance and protects the substrate from moisture.

  Furthermore, paints or coatings modified with the emulsions of the present invention can be applied to various substrates such as concrete, metal, or wood. The improved paint may be applied to one or more layers and is suitable for overcoating the applied layer. The improved paint or coating is substantially dry to the touch, exhibits rapid absorption, is easy to apply to the substrate, does not cause dewetting problems after application of the second coat, and is contact dried after application Showing gender. The improved paint or coating can also be utilized as an effective non-grafted material applied to concrete.

  In order to determine the effectiveness of the emulsions of Examples 1 and 2, examples of elastomer paints were prepared with or without a catalyst, to which the emulsions from Examples 1 and 2 were added.

The following ingredients were used during the preparation of Paint Example AI, and for various substrates plus either the emulsion of Example 1 or the emulsion of Example 2, the paint is a PVC paint. No emulsion from Example 1 or 2 was added to the control sample and Comparative Example E. The amount is expressed in grams.

  The blend of catalyst is added to Example FI and the amount is expressed in grams of catalyst / 40 g of paint.

Examples AD, FI, and Comparative Example E were prepared using the following steps.
Ingredient Nos. 1-4, and 7 are weighed and placed in a mixing vessel, then placed under a Dispermat® mixer and mixed at 100 rpm using a Dispermat® mixer, the mixer being a cooling jacket Both were set. The cooling jacket reduces emulsion breakage due to increased heat during the milling process. Ingredient No. 6 was weighed into a separate container and slowly added to the mixture and mixed for about 15 minutes until viscous. While mixing ingredients 1-4, 6 and 7, weigh ingredient numbers 9-12 into the same container, mix well, once until all dry ingredients are mixed into the mixture A spoonful of the mixture was added. The addition of the dry ingredients maintained a constant rate to allow for smoother grinding. The Dispermat® mixer was brought to 4,000 rpm and mixed for 15 minutes. The speed was adjusted as needed. It has been found desirable to increase the rate gradually to generate heat that promotes the dispersion of the components. While waiting for the dry ingredients to blend, ingredient numbers 13 and / or 14 and / or 15 are weighed into a separate container and the Dispermat® mixer is set to 2,000 rpm, with ingredient numbers 13 and Add 14 or / and 15 and mix for 5-10 minutes. Ingredient No. 16 was added and the mixture was mixed for 5 minutes. Ingredient No. 17 was weighed and Dispermat® mixer was at 1000 rpm, ingredient 17 was added to the mixture and the mixture was mixed for 5-10 minutes. Ingredient No. 5 was weighed and added to the mixture and the mixture was mixed for 5 minutes. The resulting paint formulation was labeled and poured into a cooling container for storage. Prior to applying the paint formulation to the substrate surface, the catalyst was added to Example FI as described above. Examples AD, FI, and Comparative Example E were then applied to concrete and aluminum Q panels.

  In Examples A to D and Comparative Example E, no catalyst was added, but Examples A to E showed a stable one-pack type. Examples F-I later added the catalyst to the paint system, but Examples F-I showed a two-part type with a short pot life of less than 1 hour. All Examples AD, FI, and Comparative Example E showed paints that cured at room temperature.

  The following tests were conducted for Examples AD and FI and Comparative Example E to test applied substrate cracking, appearance over time, paint or coating life, and water repellency. Mandrel flex test is performed on aluminum Q panel, water absorption is evaluated on concrete panel, water absorption of coated concrete panel is evaluated on external exposure, color QUV is monitored to observe color change, color QUV is also Outdoor exposure was also evaluated.

  The mandrel bend test is a softness and cracking test and utilized the method described in ASTM D522-93a. Paint Examples A-D, F-I, and Comparative Example E were applied to bare aluminum panels having dimensions of 7.62 x 15.24 cm (3 x 6 inches). Prior to testing, the panels were allowed to dry for 48 hours. The panel was placed vertically in the test apparatus, firmly fixed and bent within a one second time limit. The results are shown in the table below. A pass indicates that no cracks occur during the test, and a fail indicates that cracks occur during the test. All Examples AD, FI and Comparative Example E passed.

  Results of Mandell Bend test on aluminum panel Q coated with paint examples A to D, F to I, and comparative example E

  The water absorption was measured using test method ASTM D 5401. Water absorption data was collected on concrete panels of dimensions 7.62 x 15.24 cm (3 x 6 inches) coated with Paint Examples AD, FI, and Comparative Example E. Data was collected at 1 hour, 6 hours, 24 hours, 239 hours, 500 hours, 786 hours, 1000 hours, 1500 hours, 2000 hours and 2500 hours after application. Examples A2, A3, D2, D3, F2, F3, I2 and I3 showed that water penetrates the concrete in 6 hours. The water absorption of Examples AD and FI was generally comparable to acrylic and / or silicone.

  Also, a concrete panel with dimensions of 10.16 × 30.48 cm (4 × 12 inches) coated with Paint Examples A to D, F to I, and Comparative Example E for exterior testing under natural climatic conditions in Michigan. The water absorption was evaluated using ASTM D5401. The water absorption was measured after the first application and 5 months after application. In a 5-month assessment, paint example D1 shows that water penetrates the concrete within 24 hours, examples D2 and D3 blown white, examples F2 and F3 began to crumble, but soaked for 1 hour After immersion, 1 inch of the soaked bottom was intact and Example G2 began to crumble, but after soaking for 1 hour, half an inch of the soaked bottom was intact and Example G3 began to crumble but was intact. It remained. The remaining examples showed water absorption comparable to acrylic and / or silicone.

  Color QUV was monitored using a BYK colorimeter to observe the color change after each cycle. Visual evaluations were also made on concrete panels measuring 7.62 x 15.24 cm (3 x 6 inches). The elastomer silicone emulsions (Examples AD, FI) had minimal color change, while the acrylic resin of Comparative Example E was affected by yellowing. Therefore, Examples A to D and F to I showed excellent color retention as compared with the acrylic resin. The results are summarized in the following table.

In the table,
L ^* indicates brightness / darkness, L ^* = 0 is black, L ^* = 100 is scattering white, positive ΔL value is light color, negative value is dark color,
a ^* indicates red / green, positive Δa values are closer to red, negative values are closer to green,
b ^* represents yellow / blue, with positive Δb values closer to yellow and negative values closer to blue.

Examples 3-7: Preparation of another useful exemplary emulsion

  Another useful exemplary emulsion of Examples 3-7 was prepared by the above method using the following ingredients and weight percentages.

  The analysis data of Example 5 is as follows.

  To evaluate the usefulness of the emulsion as a two-part paint or coating modifier, 70% by weight of each emulsion of Examples 3-7 was mixed with 30% by weight calcium carbonate, 15.5 A combination of a catalyst with a tin content of ˜17.5% by weight (trade name: Reaxis C333W50) and a catalyst consisting of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane is then added, with a thickness of 50 mm It was applied to release paper. Examples 3-7 were evaluated in a laboratory for drying at a humidity of 77%, 21.1 ° C. (70 F) after a drying period of 7 days to determine tack, tensile strength, and elongation. Examples 3 to 7 were dried to the extent that they were touched by hand, showed no tackiness, and showed good tensile properties and elongation. See test results below.

Examples 8-17: Preparation of Another Exemplary Emulsion Another exemplary emulsion of Examples 8-17 was prepared by the method described above using the following ingredients and weight percentages.

  The analysis data of Example 13 is as follows.

  To evaluate the usefulness of the emulsion as a one-part paint or coating modifier, 70% by weight of each of the emulsions of Examples 8-17 were mixed with 30% by weight of calcium carbonate and then the emulsion. Was applied to the release paper with a thickness of 50 mm. Examples 8-17 were evaluated in a drying laboratory at a humidity of 77%, 21.1 ° C. (70 F) after a drying period of 7 days to determine tack, tensile strength, and elongation. Examples 8-13, 16 and 17 were dry to the touch, while Examples 8-12 were mild to moderately tacky and showed good tensile and elongation. Example 15 did not dry and Example 14 was dry but very sticky. The test results of Examples 8 to 17 are shown in the following table.

  Illustrative examples are described above, but these embodiments are not intended to describe all possible forms of the invention. Various embodiments may also be combined to form further embodiments of the invention.

Claims (18)

A coating or paint composition comprising the following ingredients:
(A) Silyl-terminated polymer of formula (I)

(Where
R ¹ is alkyl or aryl,
R ² is C ₁ -C ₁₂ -alkyl, H, or aryl;
X is O or NR ³ ;
R ³ is H, C ₁ -C ₁₂ -alkyl, or aryl;
Y is Si—C bonded, — (CH ₂ ) ₃ NHO (═O) —, —CH ₂ NHC (═O) —,
M is independently —CH ₂ CH ₂ —, —CH ₂ CH (CH ₃ ) —, —CH ₂ CH ₂ CH ₂ CH ₂ —, and the majority of all M is —CH ₂ CH (CH ₃ ). And
n is 0-2,
m is 1 to 500),
Optionally, (B) a silicone compound comprising a unit of the following formula (II)

(Where
a is 0-3,
b is 0-2,
c is 0, 1, 2, or 3;
R ⁴ is alkyl, aryl, aminoalkyl, glycidoxyalkyl, mercaptoalkyl,
R ⁵ is alkyl or aryl;
R ⁶ is alkyl, H, ethylene oxide, propylene oxide,
However, a + b + c is 4 or less and corresponds to oligomer, polymer and silane),
If desired
(C) an emulsifier,
(D) water,
And, if desired,
(E) catalyst,
(F) a filler, and (G) an additive. ) The coating or paint composition according to claim 1, or a combination thereof, wherein R ¹ is a methyl group, R ² is a methyl group or an ethyl group, and X is O. The coating or coating composition according to claim 1, wherein Y is —CH ₂ NHC (═O) and M is CH ₂ CH (CH ₃ ) —.   The coating or paint composition of claim 1, wherein the coating or paint composition comprises an aqueous binder.   The coating or claim 1, wherein the at least one silyl-terminated polymer is selected from the group consisting of dimethoxy (methyl) silylmethylcarbamate-terminated polyether, trimethoxysilylpropylcarbamate-terminated polyether, or blends thereof. Paint composition.   The coating or paint composition of claim 1, wherein the weight percent of the silyl terminated polymer binder is from 10 to 80 weight percent of the total emulsion weight.   The coating or paint composition of claim 1 further comprising a long chain alkylalkoxysilane.   8. A coating or paint composition according to claim 7, wherein the coating or paint composition is a coating or paint on the surface of brick, gypsum, cellulose and EIFS substrates for use in interior and / or exterior.   The coating or paint composition of claim 1, wherein the elastomeric silicone emulsion comprises a silyl-terminated polymer binder, one or more polysiloxanes, one or more emulsifiers, and water.   10. A coating or paint composition according to claim 9, wherein the one or more polysiloxanes comprise methyl substituents and / or phenyl substituents or alkyl substituents having alkoxy functionality. Mixing the emulsifier with water,
Mixing one or more silyl-terminated polymer binders into a mixture of water and an emulsifier;
Adding water,
A process for preparing an elastomeric silicone emulsion of the above formula of claim 1 comprising:   12. The method of claim 11, further comprising mixing one or more silyl terminated polymer binders and one or more polysiloxanes to make a polymer preblend.   13. The method of claim 12, wherein the polysiloxane comprises a methyl substituent and / or a phenyl substituent, or an alkyl substituent having an alkoxy functionality.   12. An improved flexibility and water repellency comprising the step of adding an elastomeric silicone resin emulsion according to claim 1 or an elastomeric silicone resin emulsion prepared by the method according to claim 11 to a coating or paint. Process for preparing an improved coating or paint composition.   The method of claim 14, wherein the coating or paint comprises an aqueous binder.   Use of a coating or paint composition according to claim 1 as an anti-graffiti paint or an improver for the anti-graffiti paint.   Use of the coating or paint composition of claim 1 in a two-component form.   The use according to claim 16, wherein the one or more catalysts are subsequently added to the coating or paint composition.